WO2006085531A1 - Catalyseur de dimérisation du propylène et méthode de dimérisation - Google Patents

Catalyseur de dimérisation du propylène et méthode de dimérisation Download PDF

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WO2006085531A1
WO2006085531A1 PCT/JP2006/302077 JP2006302077W WO2006085531A1 WO 2006085531 A1 WO2006085531 A1 WO 2006085531A1 JP 2006302077 W JP2006302077 W JP 2006302077W WO 2006085531 A1 WO2006085531 A1 WO 2006085531A1
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group
containing group
compound
transition metal
catalyst
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PCT/JP2006/302077
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English (en)
Japanese (ja)
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Jun Okuda
Yasuhiko Suzuki
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Mitsui Chemicals, Inc.
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Priority to EP06713220A priority Critical patent/EP1872853A4/fr
Priority to JP2007502610A priority patent/JP5419348B2/ja
Priority to US11/883,922 priority patent/US20080281139A1/en
Priority to CN2006800044041A priority patent/CN101115558B/zh
Publication of WO2006085531A1 publication Critical patent/WO2006085531A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/107—Alkenes with six carbon atoms
    • C07C11/113—Methylpentenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
    • C07C2/22—Metal halides; Complexes thereof with organic compounds
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C07C2/34—Metal-hydrocarbon complexes
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • the present invention relates to a propylene dimer catalyst comprising a transition metal complex compound and a method for producing 4-methyl 1 pentene using the propylene dimer catalyst.
  • dimerization of propylene has been performed under high temperature and high pressure using a solid catalyst in which an alkali metal such as sodium or potassium is supported on potassium carbonate or graphite.
  • an alkali metal such as sodium or potassium
  • nickel catalyst is well known, and since dimerization of propylene can be carried out under very mild reaction conditions, production equipment and production Cost reduction is expected, but the selectivity for 4-methyl 1-pentene production is uniformly low (see Chemical Reviews, 1991, 91-613).
  • Other transition metals and propylene dimer catalysts that give 4-methyl 1-pentene with high selectivity are uranium catalysts (see US Pat. No.
  • Patent Document 1 US Published Patent No. 4695669
  • Non-Patent Literature 1 Journal of Chemical Reviews, 1991, 91-613
  • Non-Patent Document 2 Chemistry Letter 1991 1525-1528
  • Non-Patent Literature 3 Journal of Organometallics 1992 11 ⁇ 362-369
  • Non-Patent Literature 4 Journal of Molecular Catalysis 1990 62 pp. 277-287 Disclosure of Invention
  • the present invention relates to a catalyst for propylene dimer having high activity and using a transition metal complex compound and having a high selectivity for producing 4-methyl-1-pentene, and 4-methyl using the catalyst. 1—To provide a method for producing pentene.
  • a propylene dimerization catalyst including a transition metal complex compound having a specific structure has excellent activity, and 4-methyl-1-pentene.
  • the present inventors have found that it is suitable for the production of 4-methyl-1-pentene, which has a high selectivity for producing.
  • X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a X-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a key Represents a silicon-containing group, a germanium-containing group, or a tin-containing group, and the groups represented by X may be the same or different from each other, and the groups represented by X are bonded to each other to form a ring. May be. In the formula, the dotted line indicates a coordination bond. )
  • transition metal complex compound [A1] group power consisting of compounds that form an ion pair Propylene dimerization according to any one of [1] to [4], including at least one selected compound Provision of catalysts.
  • Ml represents a transition metal atom in Groups 3 to 11 of the periodic table other than lanthanoid atoms and actinoid atoms
  • n represents the valence of Ml
  • X represents a hydrogen atom, a halogen atom, a hydrocarbon group, Oxygen-containing group, nitrogen-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, keyium-containing group, germanium-containing group, or tin-containing
  • a group represented by X may be the same as or different from each other, and groups represented by X may be bonded to each other to form a ring, and the dotted line represents a coordination bond. .
  • Transition metal complex compound A group power consisting of a compound that reacts with [A2] to form an ion pair. Proposal of a catalyst for propylene dimerization containing at least one selected compound
  • Ml of the transition metal complex compound [A2] represented by the general formula (IV) is a hafnium or a zirconium atom.
  • [9] It is to provide a process for producing 4 methyl 1 pentene in which propylene is dimerized in the presence of the propylene dimer catalyst as described in [1] to [8].
  • [Al] [A2] may be collectively referred to as [A]
  • [Bl] [B2] may be collectively referred to as [B].
  • (bl-1) (b2-l) etc. may be collectively referred to as (b-l) etc.
  • the present invention provides a catalyst for propylene dimer soot having high activity. Furthermore, according to the propylene dimerization technology according to the present invention, 4-methyl-1-pentene can be produced with high activity and selectivity. Furthermore, in the resulting propylene dimer, When polymerizing 4-methyl-l-pentene in the presence of a polymerization catalyst such as a titanium catalyst or a meta-catacene catalyst, the amount of components that inhibit the polymerization is small, and this is extremely industrially valuable. .
  • a polymerization catalyst such as a titanium catalyst or a meta-catacene catalyst
  • the propylene dimer catalyst for use in the present invention comprises: [A1] a transition metal complex compound represented by the general formula (I) and, if necessary,
  • (bl-3) Transition metal complex compound This compound is formed from at least one compound selected from the group consisting of compounds that react with [A1] to form ion pairs.
  • the dimerization reaction is preferably carried out using a catalyst in which not only the [A1] component but also the [B1] component coexists.
  • the catalyst for propylene dimer soot according to the present invention includes: [A2] a transition metal complex compound represented by the general formula (I), and
  • Transition metal complex compound It is formed from at least one compound selected from the group force consisting of compounds that react with [A2] to form ion pairs.
  • a compound that reacts with the transition metal complex compound [A] to form an ion pair may be referred to as an “ionized ionic compound” t.
  • the transition metal complex compound [Al] [A2] of the present invention is a transition metal complex compound represented by the following general formulas (1) and ( ⁇ ).
  • ⁇ to 1 ⁇ 1 () may be the same or different from each other, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group , Boron-containing group, aluminum-containing group, iodo-containing group, phosphorus-containing group, kaium-containing group, germanium-containing group, or tin-containing group, and two or more of them are connected to each other to form a ring. Forming A little.
  • R 1 -R is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, or an acyl group.
  • examples of the halogen atom include fluorine, chlorine, bromine, and iodine.
  • the hydrocarbon group has 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec butyl, tert-butynole, neopentyl, n-hexyl, etc.
  • a linear or branched alkenyl group having 2 to 20 a linear or branched alkyl group having 2 to 30, preferably 2 to 20 carbon atoms such as ethynyl and propargyl
  • Cyclic saturated hydrocarbons having 3 to 30, preferably 3 to 20 carbon atoms such as propyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl
  • carbon sources such as cyclopentagel, indul and fluorine Cyclic unsaturated hydrocarbon group having 5 to 30 atoms; having 6 to 30, preferably 6 to 20 carbon atoms such as phenol, benzyl, naphthyl, biphenyl, terphel, phenanthryl and anthracel Aryl groups;
  • the hydrocarbon group may have a hydrogen atom substituted with a halogen atom.
  • the hydrocarbon group has 1 to 30 carbon atoms such as trifluoromethyl, pentafluorophenyl, and black-mouthed phenol. Or 1 to 20 halogenated hydrocarbon groups.
  • examples of the hydrocarbon group may include an aryl group-substituted alkyl group such as benzyl or Tamyl, in which a hydrogen atom may be substituted with another hydrocarbon group.
  • the hydrocarbon group may be a heterocyclic compound residue; an alkoxy group, an alkyl group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydride group.
  • Oxygen-containing groups such as loxy group, peroxy group, carboxylic acid anhydride group; amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanic acid
  • Nitrogen-containing groups such as ester groups, amidino groups, diazo groups, and amino groups in the form of ammonium salts; Boron-containing groups such as boranezyl groups, borantylyl groups, diboraryl groups; mercapto groups, thioester groups, dithioesters Group, alkylthio group
  • 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butynole, neopentyl, n-hexyl, adamantyl, etc.
  • a substituted aryl group or the like in which 1 to 5 substituents such as 6 to 30, preferably 6 to 20 aryl groups or aryloxy groups are substituted is preferable.
  • Heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran, residues such as sulfur-containing compounds such as thiophene, And a group obtained by further substituting a substituent such as an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, to these heterocyclic compound residues.
  • nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine
  • oxygen-containing compounds such as furan and pyran
  • residues such as sulfur-containing compounds such as thiophene
  • a substituent such as an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms
  • the oxygen-containing group, nitrogen-containing group, xio-containing group and phosphorus-containing group shown as 1 ⁇ to 1 ⁇ ° are the same as those exemplified as the substituent which may be contained in the hydrocarbon group. Things.
  • the boron-containing group may be contained in the above hydrocarbon group, but may be the same as those exemplified as the substituent, as well as an alkyl group-substituted boron, aryl group-substituted boron, boron halide, alkyl group-substituted halogen group. Examples include groups such as boron.
  • Alkyl group substituted boron includes (Et) B-, (iPr) B-, (iBu) B-, (Et) B, (iPr) B, (iBu) B;
  • Examples of boron include (Et) BCl, (iBu) BCl—, (C H) BC1 and the like. Three of these
  • the substituted boron may be in a coordinated state.
  • Et represents an ethyl group
  • iPr represents an isopropyl group
  • iBu represents an isobutyl group.
  • Alkyl-substituted aluminum includes (Et) Al—, (iPr) Al—, (iBu) Al
  • A1-; Aluminum halide includes A1C1-, A1C1; Alkyl group-substituted neurogen
  • Examples of aluminum fluoride include (Et) AlCl—, (iBu) A1C1—, and the like. Of these, tri-substituted aluminum may be in a coordinated state.
  • Et represents an ethyl group
  • iPr represents an isopropyl group
  • iBu represents an isobutyl group.
  • Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group.
  • Specific examples of the hydrocarbon-substituted silyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, jetylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, And dimethyl (pentafluorophenyl) silyl.
  • methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, jetylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly preferred are trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenolyl.
  • Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy and the like.
  • germanium-containing group and the tin-containing group the above-described group-containing group is gelled. Examples thereof include those substituted with manium and tin.
  • amide groups include acetoamide, N-methylacetamide, N-methylbenzamide and the like.
  • Amino groups include dimethylamidoethylmethylamino, diphenylamino and the like as imide groups.
  • Preferred examples of the force imino group such as acetoimide and benzimide include methylimino, ethylimino, propyliminobutylimino, and phenylomino.
  • thio-containing groups methylthio, ethylthio and the like are alkylthio groups, phenylthio, phenylphenylthio, naphthylthio and the like are arylthio groups, and acetyl groups are acetylthio, benzoylthio, Forces such as methylthiocarbol and phenol thiol
  • sulfone ester group methyl sulfonate, ethyl sulfonate, phenyl sulfonate, etc.
  • the sulfonamide group phenyl sulfonamide, N-methylsulfonamide
  • Preferable examples include N-methyl-p-toluenesulfonamide.
  • ⁇ 1 to! ⁇ are a group in which two or more of these groups, preferably adjacent groups, are linked to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. Therefore, these rings may further have a substituent.
  • Ml represents a transition metal atom of Group 3 of the periodic table other than lanthanoid atoms and actinoid atoms: specifically, zirconium, titanium, hafnium, vanadium Niobium, tantalum, chromium, molybdenum or tungsten, preferably zirconium, titanium or hafnium, more preferably zirconium or hafnium, particularly preferably hafnium.
  • N is the valence of Ml.
  • X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a X-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, It represents a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group.
  • examples of the halogen atom include fluorine, chlorine, bromine, and iodine.
  • hydrocarbon group examples include those similar to those exemplified for R ⁇ R in the general formula (I). Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; cycloalkyl having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl Groups; alkenyl groups such as butyl, probe, and cyclohexenyl; aryl alkyl groups such as benzyl, phenyl, and propyl; fur, tolyl, dimethylphenol, trimethylphenol, and ethylphenol Forces including aryl groups such as -l, propylphenol, biphenyl, naphthyl, methylnaphthyl, anthryl, phenanthryl, etc.
  • alkyl groups such
  • hydrocarbon groups include halogen-substituted hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 30 carbon atoms is substituted with halogen. Of these, those having 1 to 20 carbon atoms are preferred.
  • heterocyclic compound residue examples include the same as those exemplified for 1 ⁇ to 1 ⁇ ° of the general formula (I).
  • oxygen-containing group examples are the same as those exemplified for 1 ⁇ to 1 ⁇ ° of the general formula (I), specifically, hydroxy groups; alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, etc. Groups; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; aryloxy groups such as phenylmethoxy and phenylethoxy; forces such as methoxy groups; carbonyl groups, etc. Absent.
  • Examples of the thio-containing group are the same as those exemplified for R ⁇ R in the general formula (I), and specifically include methyl sulfonate, trifluoromethane sulfonate, and phenol. -Nolesno sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate, triisobutyl benzene sulfonate, p-chronole benzene sulfonate, pentafluorobenzene sulfonate, etc.
  • Sulfonate groups such as methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene sulfinate; alkylthio groups; arylthio groups, etc. Forces limited to these Not to.
  • nitrogen-containing group examples include the same groups as those exemplified for ⁇ 1 ⁇ ° of the general formula (I).
  • Specific examples include an amino group; Forces that include alkylamino groups such as dipropylamino-containing dibutylamino and dicyclohexylamino; phenylamine-containing diphenylamine-containing ditolylaminated dinaphthylamino, methylphenolamino and other arylamino groups and alkylarylamino groups, etc. is not.
  • boron-containing group examples include BR (R represents hydrogen,
  • a kill group an aryl group which may have a substituent, a halogen atom, etc.
  • phosphorus-containing groups include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tritolylphosphine; methyl phosphite, ethyl phosphite, fluorine Forces including phosphite groups (phosphide groups) such as ennenore phosphite; phosphonic acid groups; phosphinic acid groups and the like.
  • trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine
  • triarylphosphine groups such as triphenylphosphine and tritolylphosphine
  • silicon-containing group examples include those similar to those exemplified in the general formula (I) at ⁇ 1 ⁇ °.
  • Specific examples include phenylsilyl, diphenylsilyl, and trimethylsilyl.
  • Hydrocarbon substituted silyl groups such as triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tolylsilyl, trinaphthylsilyl, etc .
  • hydrocarbon substituted silyl ether groups such as trimethylsilyl ether; trimethylsilyl methyl, etc.
  • a silicon-substituted alkyl group such as trimethylsilylphenyl.
  • germanium-containing group examples include the same groups as those exemplified for 1 ⁇ to 1 ⁇ ° of the general formula (I). A group in which is substituted with germanium.
  • tin-containing group examples include the same ones as exemplified in 1 ⁇ to 1 ⁇ ° of the general formula (I). More specifically, tin in the above-described group containing a group is substituted with tin.
  • halogen-containing group examples include fluorine-containing groups such as PF and BF, CIO, and SbCl.
  • AIR has hydrogen, an alkyl group, and a substituent.
  • a force such as a aryl group or a halogen atom) is not limited thereto.
  • halogen atoms and alkyl groups are preferred, and chlorine, bromine and methyl groups are preferred.
  • transition metal complex compound [A] represented by the general formulas (1) and ( ⁇ ) is, for example, Orga nometallics magazine, 1985, April 97-104 or Macromolecules magazine, 2000, 33, 7 54- This is performed in accordance with the method described on page 759.
  • the reaction product can be used as a mixture without performing a purification operation, or can be used by being purified by a purification operation such as recrystallization.
  • Component [B] reacts with (b-1) organometallic compound, (b-2) organoaluminum compound, and (b-3) transition metal complex compound [A]. It is at least one compound selected from the group force consisting of compounds that form ion pairs.
  • the component [B] is a force used as necessary.
  • the transition metal complex compound [A2] represented by II) is used, the [B] component is essential, the (B 2-1) organometallic compound and (b2-3) transition metal as the [B2] component.
  • At least one compound selected from the group consisting of compounds that react with the complex compound [A2] to form an ion pair is used.
  • [B2] component when [A2] component is used (b2-1) component only, (b2-3) component only, (b2-1) component and (b2-3) component Only, and those obtained by caloric-excluding the component (b2-2).
  • the (b-1) organometallic compound used in the present invention include the following organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table. Light up.
  • the (b-1) organometallic compound of [B] does not include the (b 2) organoaluminum compound described later.
  • mnpq May represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms
  • X represents a halogen atom
  • m is 0 ⁇ m ⁇ 3
  • n is 0 ⁇ n ⁇ 3
  • p is 0 ⁇ p ⁇ 3
  • q is a number 0 ⁇ q ⁇ 3
  • m + n + p + q 3
  • R a and R b may be the same or different and each have 1 to 15, preferably 1 to 4 carbon atoms
  • organoaluminum compound belonging to the above (b-la) examples include the following compounds.
  • R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 ⁇ m ⁇ 3).
  • Organoaluminum compound, general formula R a A1H (where R a is a hydrocarbon having 1 to 15 carbon atoms, preferably 1 to 4 m 3 to m
  • a hydrocarbon group having 1 to 15, preferably 1 to 4 atoms, X represents a halogen atom, m is 0 ⁇ m ⁇ 3, n is 0 ⁇ n ⁇ 33, q is 0 ⁇ q ⁇ 3 And an aluminum compound represented by m + n + q 3.
  • organoaluminum compounds belonging to (b-la) more specifically, trimethylaluminum, triethylaluminum, tri (n-butyl) aluminum, tripple pillaluminum, tripentylaluminum, Tri (n-alkyl) aluminum such as xylaluminum, trioctylaluminum, tridecylaluminum; triisopropylaluminum, triisobutylaluminum, tri (sec-butyl) aluminum, tri (tert-butyl) aluminum, tri (2 —Methylbutyl) aluminum, tri (3-methylbutyl) aluminum, tri (2-methylpentyl) aluminum, tri (3-methylpentyl) aluminum, tri Tri-branched alkyl aluminum such as (4-methylpentyl) aluminum, tri (2-methylhexyl) aluminum, tri (3-methylhexyl) aluminum, tri (2-ethylhexyl) aluminum; tricyclohexylalumin
  • Alkenyl aluminum such as isoprenylaluminum represented by the following: alkylaluminum alkoxide such as isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide; dimethylaluminum methoxide, jetylaluminum ethoxide, dibutylaluminum butoxide Dialalkylaluminum alkoxides such as; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; R a Al (OR b ) (
  • R a and R b each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other.
  • Etc. partially alkylated alkylaluminum having an average composition represented by, for example: jetyl aluminum phenoxide, jet aluminum (2,6 di-tert-butyl-4-methyl phenoxide), ethyl aluminum bis (2, 6 di-tert-butyl-4-methylphenoxide), diisobutylaluminum (2, 6-di-tert-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-tert-butyl-4-methylphenoxide), etc.
  • Dialkylaluminum bite oxides Dialkylaluminum halides such as dimethylaluminum chloride, jetylaluminum chloride, dibutylaluminum chloride, jetylaluminum bromide, diisobutylaluminum chloride; Alkysesium halides, alkylaluminum sesquihalides such as ethylaluminum sesquibromide; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; Dialkylaluminum hydrides such as tilaluminum hydride and dibutylaluminum hydride; Ethylaluminum dihydride and propylaluminum Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as mudihydride; Partially alkoxylated and
  • a compound similar to (b-la) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such compounds include (C H) A1N (C H) A1 (C H).
  • Examples of the compound belonging to (b-lb) include LiAl (C H) and LiAl (C H).
  • organometallic compounds include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium.
  • Tubum mouth amide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylenomagnesium, jetinolesmagnesium, dibutinomagnesium, butylethylmagnesium, and the like can also be used.
  • a compound that can form the organoaluminum compound in the dimer system for example, a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium. It can also be used.
  • organometallic compounds organoaluminum compounds are preferred.
  • the above (b-1) organometallic compounds are used singly or in combination of two or more.
  • the (b-2) organoaluminum compound used as necessary in the present invention may be a conventionally known aluminoxane or benzene as exemplified in JP-A-2-78687. It may be an insoluble organoaluminum compound.
  • the conventionally known aluminoxane can be produced, for example, by the following method and is usually obtained as a solution in a hydrocarbon solvent.
  • a compound containing adsorbed water or a salt containing water of crystallization, such as sodium chloride magnesium hydrate, copper sulfate hydrate, sulfate Adsorbed water by adding an organoaluminum compound such as trialkylaluminum to a hydrocarbon medium suspension such as lumidium hydrate, nickel sulfate hydrate, or cerium chloride hydrate.
  • a method of reacting crystal water with an organoaluminum compound is usually obtained as a solution in a hydrocarbon solvent.
  • the aluminoxane may contain a small amount of an organometallic component.
  • the recovered solvent solution of the above aluminoxane or the unreacted organoaluminum compound may be removed by distillation, and then redissolved in a solvent or suspended in a poor solvent for aluminoxane.
  • Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organic aluminum compounds as those exemplified as the organoaluminum compound belonging to the above (b-la).
  • trimethylaluminum is particularly preferred, with trialkylaluminum and tricycloalkylaluminum being preferred! /.
  • organoaluminum compounds may be used alone or in combination of two or more.
  • Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, tamen, and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane.
  • aromatic hydrocarbons such as benzene, toluene, xylene, tamen, and cymene
  • aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane.
  • the A1 component dissolved in benzene at 60 ° C is usually 10% or less, preferably 5% or less in terms of A1 atom.
  • those having a content of 2% or less, that is, insoluble or hardly soluble in benzene are preferred.
  • organoaluminum oxide compound used in the present invention also include an organoaluminum oxide compound containing boron represented by the following general formula (i).
  • R 11 represents a hydrocarbon group having 1 to: LO carbon atoms.
  • R 12 represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 110 carbon atoms, which may be the same or different from each other.
  • the organoaluminum compound containing boron represented by the general formula (i) is an alkyl boronic acid represented by the following general formula (ii):
  • alkyl boronic acid represented by the general formula (ii) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n butyl boronic acid, isobutyl boronic acid, n xyl boronic acid. Cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5 bis (trifluoromethyl) phenylboronic acid, and the like.
  • methyl boronic acid n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable.
  • organoaluminum compound to be reacted with such an alkylboronic acid As an organoaluminum compound to be reacted with such an alkylboronic acid, And organic aluminum compounds similar to those exemplified as the organoaluminum compounds belonging to (B-la). Of these, trialkylaluminum and tricycloaluminum are preferred, especially trimethylaluminum, triethylaluminum and triisobutylaluminum. These may be used alone or in combination of two or more.
  • the transition metal complex compound [A] is decamethylnofunocene dichloride and decamethylzirconocene dichloride, the organoaluminum oxide compound (b-2) is not used.
  • the compound (b-3) that reacts with the transition metal complex compound [A] to form an ion pair which is used as necessary in the present invention, reacts with the transition metal complex compound [A] to form an ion pair. It is a compound. Therefore, the compound which forms an ion pair by contacting at least with the transition metal complex compound [A] is included in this compound.
  • Examples of such compounds include JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-3-307704, US Pat. No. 5,321,106, and the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.
  • BR is fluorine, methyl group, trifluoromethyl group
  • Examples thereof include trifluoroboron, triphenylpolone, tris (4 fluorophenyl) boron, and tris ( 3,5-difluorophenol) boron, tris (4fluoromethylphenol) boron, tris (pentafluorophenol) boron, tris (p-tolyl) boron, tris (o-tolyl) boron , Tris (3,5-dimethylphenol) boron and the like.
  • Examples of the ionic compound include compounds represented by the following general formula (III):
  • examples of R 13+ include H +, carbo-um cation, oxo-um cation, ammonium cation, phospho-um cation, cycloheptyl aryl cation, and phlegm cation cation having a transition metal. .
  • R 13 to R 17 are organic groups which may be the same or different from each other, preferably an aryl group or a substituted aryl group.
  • carbo cation examples include tri-substituted carbo cation such as triphenyl carbo cation, tri (methyl phen) carbo cation and tri (dimethyl phen) carbo cation. It is done.
  • ammonium cation examples include trialkyl ammonium cation such as trimethyl ammonium cation, triethyl ammonium cation, tri (n-propyl) ammonium cation, and tri (n-butyl) ammonium cation; N, N, N-dialkyl arium cations such as N-dimethyl-rium cation, N, N-jetyl-rium cation, N, N, 2, 4, 6-pentamethyl arium cation; di (isopropyl) ammonium cation And dialkyl ammonium cations such as dicyclohexyl ammonium cations.
  • trialkyl ammonium cation such as trimethyl ammonium cation, triethyl ammonium cation, tri (n-propyl) ammonium cation, and tri (n-butyl) ammonium cation
  • N, N, N-dialkyl arium cations such as N
  • Specific examples of the phosphonium cation include a triphenyl phosphonium cation and a triphenyl cation.
  • triarylphosphonium cations such as (methylphenol) phosphonium cation and tri (dimethylphenol) phosphonium cation.
  • R 13+ is preferably a carbonium cation, an ammonium cation, or the like, particularly a triphenyl carbonate cation, an N, N-dimethylarium cation, or an N, N-jetylarium cation.
  • Examples of the ionic compound also include trialkyl-substituted ammonium salts, N, N-dialkylammonium salts, dialkylammonium salts, and triarylphosphonium salts.
  • Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetraphenol, tri (n-propyl) ammonium tetraphenol, tri (n-butyl) ammonium tetraphenol, trimethylammonium.
  • Umtetra (p-tolyl) borate trimethylammonium tetra (o-tolyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenol) borate, tri (n-propyl) ammo- Umtetra (o, p-dimethylphenol) borate, tri (n-butyl) ammotetra (m, m-dimethylphenol) borate, tri (n-butyl) ammotetra (p-trifluoromethylphenol) B) Borate, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenol) borate, tri (n-butynole) ammoumte (O- Torinore) borate.
  • N, N-dialkyla-linum salt examples include, for example, N, N-dimethyla-Ryu tetratetraoleporate, N, N-deethylaureum tetraphenolate, N, N, 2, 4, 6— Examples include pentamethylayuyl tetraphenol.
  • dialkyl ammonium salt examples include di (n-propyl) ammonium tetra (pentafluorophenol) borate and dicyclohexyl ammonium tetraphenyl borate.
  • Et represents an ethyl group.
  • borane compound examples include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butynole) ammonium] decaborate, bis [tri (n-butyl) Amionum undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecacat Salt; Tri (n-butyl) ammonium bis (dode hydride dodecaborate) cobaltate ( ⁇ ), bis [tri (n-butyl) ammonum] bis (dode hydride dodecaborate) nickel acid Metal borane-on salts such as salt ( ⁇ ).
  • carborane compound examples include, for example, 4 one-strength ruvanonaborane (14), 1,3-dicarpanonaborane (13), 6, 9 dicarbadecarborane (14), dodecahydride 1 Hue 2 Lou 1, 3 Dicarpanonaborane, Dodeca Hydride 1-Methyl-1, 3 Dicarba Nonaborane, Unde Force Hydride 1, 3 Dimethyl 1, 3 Dicarpanonaborane, 7, 8 Dicarounde Force Boran (13), 2, 7 Dicarounde Force Borane (13), Wunde Force Hydride 7, 8—Dimethyl-7, 8—Dicarounde Force Borane, Dodeca Hydride 11-Methyl-2, 7 Dicarounde Force Borane, Tri (n-Butyl) Ammonium 1 Cal Badecaborate, Tri (n— Butyl) ammonium 1 Carounde force borate, tri (n-butyl) ammonium 1 One-strand rubadodecabor
  • Heteropoly compounds also include atoms that can also be made of silicon, phosphorus, titanium, germanium, arsenic, or tin, and one or more nuclear powers that can also select vanadium, niobium, molybdenum, and tungsten.
  • heteropoly compound and the isopoly compound are not limited to one of the above compounds, and two or more of them can be used.
  • a propylene dimer can be obtained with high and dimer activity and, in particular, the selectivity of 4-methyl-1 pentene is high.
  • an organoaluminum compound (b-2) such as methylaluminoxane as a promoter component
  • b-3 an organoaluminum compound
  • ionized ion compound (B-3) such as triphenyl carbonate tetrakis (pentafluorophenol) borate
  • 4 methyl is obtained with good activity and very high selectivity.
  • the catalyst for propylene dimerization according to the present invention includes a transition metal complex compound [A], if necessary (b-1) an organometallic compound, and (b-2) an organoaluminum oxide.
  • a carrier [C] as described later may be used as necessary.
  • the carrier used as necessary in the present invention is an inorganic or organic compound, and is a granular or particulate solid.
  • the inorganic compound porous oxides, inorganic chlorides, clays, clay minerals, or ion-exchangeable layered compounds are preferable.
  • porous oxide specifically, SiO, Al 2 O, MgO, ZrO, TiO, B 2 O, CaO,
  • SiO 2 —Cr 2 O 3 SiO 2 —TiO 2 —MgO, or the like can be used. Of these, SiO
  • the inorganic oxide contains a small amount of NaCO, KCO, CaCO, MgCO, NaSO,
  • Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 ⁇ m, preferably 20 to 200 ⁇ m, and has a specific surface area. Is from 50 to L000 m 2 / g, preferably from 100 to 700 m 2 / g, and the pore volume is preferably from 0.3 to 3. Ocm 3 Zg. Such carriers are 100-1000 as required. C, preferably baked at 150 to 700 ° C.
  • inorganic chloride MgCl, MgBr, MnCl, MnBr and the like are used.
  • inorganic chloride MgCl, MgBr, MnCl, MnBr and the like are used.
  • the product may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a solution in which inorganic chloride is dissolved in a solvent such as alcohol and then precipitated in the form of fine particles with a precipitating agent.
  • the clay used as a carrier in the present invention is usually composed mainly of a clay mineral.
  • the ion-exchange layered compound used as a carrier in the present invention is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak binding force, and ions contained therein It can be exchanged.
  • Most clay minerals are ion-exchange layered composites.
  • these clays, clay minerals, and ion-exchange layered compounds are not limited to natural ones, and artificial compounds can also be used.
  • clay clay mineral or ion-exchange layered composite
  • clay, clay mineral, or layered crystal structure such as hexagonal close packing type, antimony type, CdCl type, Cdl type, etc.
  • examples thereof include ionic crystalline compounds having
  • clays and clay minerals examples include kaolin, bentonite, kibushi clay, gyrome clay, alofen, hisingelite, neurophyllite, unmo group, montmorillonite group, vermiculite, lyotadi stone group, norgorskite, kaolinite, nacrite. , Datekite, halloysite, etc., and the ion-exchange layered compound includes a—Zr (HAsO) ⁇ ⁇ 0,
  • Examples include crystalline acid salts of divalent metals.
  • Such a clay, clay mineral, or ion-exchange layered compound is preferably one having a pore volume of 20 angstroms or more measured by mercury porosimetry and 0.1 ccZg or more. Those of ⁇ 5 ccZg are particularly preferred.
  • the pore volume is measured in a pore radius range of 20 to 3 ⁇ 10 4 angstroms by mercury porosimetry using a mercury porosimeter.
  • a carrier having a pore volume of 20 angstroms or more and a pore volume smaller than 0.1 lcc / g is used as a carrier, it tends to be difficult to obtain high dimer activity.
  • the clay and clay mineral used in the present invention are preferably subjected to chemical treatment.
  • Any chemical treatment can be used, such as a surface treatment that removes impurities adhering to the surface, or a treatment that affects the crystal structure of the clay.
  • Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment.
  • acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure.
  • Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay.
  • an ionic complex, a molecular complex, an organic derivative, etc. can be formed, and the surface area and interlayer distance can be changed.
  • the ion-exchangeable layered composite used in the present invention utilizes the ion-exchange property, and exchanges the exchangeable ions between the layers with other large and bulky ions, thereby expanding the layers. It may be a composite. Such bulky ions play a role of supporting pillars and are usually called pillars.
  • intercalation Guest compounds that intercalate include cationic inorganic compounds such as TiCl and ZrCl, Ti (OR), and Zr (OR) , PO (OR), B (OR) and other metal alkoxides (R is a hydrocarbon group, etc.), [Al O (OH)
  • colloidal inorganic compounds such as SiO can coexist. Also, let's say
  • Examples thereof include an oxide produced by heat dehydration after intercalation of the metal hydroxide ions between layers.
  • the clay, clay mineral, and ion-exchange layered composite used in the present invention may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing water or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more.
  • clays or clay minerals preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, theolite and synthetic mica.
  • Examples of the organic compound include granular or particulate solids having a particle size in the range of 10 to 300 ⁇ m.
  • (co) dimeric rods or bulucycloforms which are produced mainly from ⁇ -olefins with 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, 4-methylone, and pentene.
  • Examples thereof include (co) dimeric rods produced mainly from xylene and styrene, and modified products thereof.
  • the propylene dimer catalyst according to the present invention comprises the transition metal complex compound [ ⁇ ], if necessary (b-1) an organometallic compound, and (b-2) an organoaluminum compound. And (b 3) at least one compound selected from ionized ionic properties (B), and optionally a carrier [C], and, if necessary, a specific organic compound [D ]
  • the [D] organic compound component is used for the purpose of improving dimer performance as required.
  • organic compounds include alcohols, phenolic compounds.
  • Powers including compounds, carboxylic acids, phosphorus compounds and sulfonates are not limited thereto.
  • R 18 — OH As the alcohols and phenolic compounds, those represented by R 18 — OH are usually used (where R 18 is a hydrocarbon group having 1 to 50 carbon atoms or 1 to 50 carbon atoms). As the alcohols, those in which R 18 is a halogenated hydrocarbon are preferable.
  • phenolic compound those in which the ⁇ , ⁇ , 1-position of the hydroxyl group is substituted with a hydrocarbon having 1 to 20 carbon atoms are preferable.
  • R 19 represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, particularly preferably a halogenated hydrocarbon group having 1 to 50 carbon atoms.
  • M is an element of Groups 1 to 14 of the periodic table.
  • R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
  • X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
  • m is an integer from 1 to 7
  • n is the valence of M, and l ⁇ n ⁇ 7.
  • the propylene dimerization method according to the present invention comprises dimerizing propylene in the presence of the catalyst.
  • dimerization the method of adding component [A] to the reactor, the usage of each component, the addition method, and the order of addition are arbitrarily selected. The following methods are exemplified.
  • Component [A] and (b-1) an organometallic compound, (b-2) an organoaluminum oxide compound, and (b-3) an ionized ionic compound force are also selected.
  • component [A] and component [B] are contacted in advance, and component [B] is added to the reactor in any order.
  • component [B] may be the same or different.
  • component [A] and component [B] are supported on a carrier [C] and a catalyst component and component [B] are added to the reactor in any order.
  • component [B] may be the same or different
  • component [B] is supported on support [C]
  • the catalyst component, component [A], and component [B] are added to the reactor in any order.
  • component [B] may be the same or different
  • component [A] is supported on support [C]
  • component [B] is supported on support [C]
  • component [B] is added to the reactor in any order.
  • component [B] may be the same or different.
  • component [A], component [B] and component [D] are contacted in advance, and component [B] is added to the reactor in any order.
  • component [B] may be the same or different.
  • 4-methyl-1-pentene is obtained by diluting propylene in the presence of the propylene dimerization catalyst as described above.
  • the dimerization can be carried out even in a liquid phase reaction method such as a dissolution reaction or a suspension reaction or a gas phase reaction method.
  • the inert hydrocarbon medium used in the liquid phase dimerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane , Cyclohexane, methylcyclopentane, and other alicyclic hydrocarbons; benzene, toluene, xylene, and other aromatic hydrocarbons; ethylene chloride, chlorobenzene, dichloromethane, and other halogenated hydrocarbons, and mixtures thereof Propylene itself can also be used as a solvent.
  • aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene
  • cyclopentane Cyclohexane, methylcyclopentane, and other
  • component [A] is 1 liter of the reaction volume, usually 10- 12 ⁇ : LO- 2 moles , used in such an amount that preferably a 10- 1Q to 10-3 moles.
  • component [A] is used at a relatively low concentration, it is possible to diminish propylene with high dimer activity.
  • component (b-1) is converted into a molar ratio of component (b-1) to the transition metal complex atom (Ml) in component [A] [(b- 1) ZM1] Force Usually 0.01 ⁇ : LOOOOO, preferably 0.05 ⁇ 50000.
  • Component (b-2) consists of aluminum atoms in component (b-2) and transition metal atoms in component [A].
  • Component (b-3) contains a molar ratio of component (b-3) to the transition metal atom (Ml) in component [A] [(b)
  • ZM1] is usually used in an amount of 1 to 10, preferably 1 to 5.
  • component [D] has a molar ratio [(D) Z (b-1)] of from 0.01 to 10, preferably 0.1.
  • component [D] in an amount of ⁇ 5
  • component [D] in an amount such that the molar ratio [(D) Z (b-2)] to the aluminum atom is usually 0.001 to 2, preferably 0.005 to 1.
  • the molar ratio [(0) 70) 3) is usually 0.01 to 10, preferably 0.1 to 5.
  • the dimer temperature of propylene using such a propylene dimer catalyst is usually
  • the reaction pressure is usually from normal pressure to 100 kg / cm 2 , preferably from normal pressure to 50 kg / cm 2 , and the dimerization reaction is a batch, semi-continuous or continuous method. You can even do it.
  • the mass of the reaction product obtained per unit time was obtained by dividing the mass of the transition metal atom (mmol) in the transition metal catalyst component used for the polymerization.
  • the selectivity for 4-methyl-1 pentene was determined according to the following formula.
  • transition metal compound according to the present invention is shown below, and specific examples and comparative examples of propylene dimerization are shown.
  • the dimerization reaction was started by adding 0.008 mmol of (tetrahydrothiophene). In a propylene gas atmosphere (gauge pressure 100 kPa), the reaction was carried out at 50 ° C for 30 minutes, and then the reaction was stopped by adding a small amount of methanol. After completion of the reaction, low-boiling components (carbon atoms of 10 or less) were separated from high-boiling components under reduced pressure and analyzed using gas chromatography. The catalytic activity was 0.7 g of product Z (mmol-Hf'h), and 4-methyl-1 pentene selectivity of the product was 33%.
  • low-boiling components (10 or less carbon atoms) were separated from high-boiling components under reduced pressure and analyzed using gas chromatography.
  • the catalytic activity was 719 g of product Z (mmol-Hf'h), and 4-methyl-1-pentene among the products was 35%.
  • Examples 2, 4, 6, 8, 10, and 12 were carried out according to the conditions described in Comparative Example 2 except that the transition metal compounds were changed to the compounds described in Table 1.
  • Examples 3, 5, 7, 9, 11, and 13 were carried out according to the conditions described in Example 1 except that the transition metal compounds were changed to the compounds described in Table 1. The results are shown in Table 1.
  • the reaction was carried out in the same manner as in Example 1 except that the transition metal compound represented by the following g obtained in Synthesis Example 7 was used instead of decamethylnofunocene dichloride.
  • the catalytic activity was 233 g of product Z (mmol-Zr ⁇ h), and the selectivity of 4 methyl 1 pentene among the products was 45%.
  • the catalyst for propylene dimerization according to the present invention is characterized by having an excellent activity and a high selectivity for producing 4-methyl-1 monopentene. Therefore, the propylene dimerization catalyst and quantification method of the present invention are expected to make a great industrial contribution in fields where 4-methyl-11-pentene is required to be produced efficiently.

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Abstract

La présente invention porte sur un catalyseur de dimérisation du propylène présentant une activité de dimérisation du propylène très élevée. La présente invention porte également sur une méthode de synthèse du 4-méthyl-1-pentène employant un tel catalyseur. La présente invention concerne plus spécifiquement un catalyseur de dimérisation du propylène contenant un composé de type complexe de métal de transition [A], au moins un composé [B] sélectionné au sein du groupe constitué des composés organométalliques (b-1), des composés de type oxydes d'organoaluminium (b-2) et des composés (b-3) formant une paire d'ions par réaction avec le composé de type complexe de métal de transition [A]. La présente invention concerne en outre spécifiquement une méthode de dimérisation du propylène employant un tel catalyseur.
PCT/JP2006/302077 2005-02-10 2006-02-07 Catalyseur de dimérisation du propylène et méthode de dimérisation WO2006085531A1 (fr)

Priority Applications (4)

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EP06713220A EP1872853A4 (fr) 2005-02-10 2006-02-07 Catalyseur de dimérisation du propylène et méthode de dimérisation
JP2007502610A JP5419348B2 (ja) 2005-02-10 2006-02-07 プロピレン二量化用触媒および二量化方法
US11/883,922 US20080281139A1 (en) 2005-02-10 2006-02-07 Catalyst for Propylene Dimerization and Dimerization Method
CN2006800044041A CN101115558B (zh) 2005-02-10 2006-02-07 丙烯二聚化用催化剂和二聚化方法

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JP2005034059 2005-02-10

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EP (1) EP1872853A4 (fr)
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KR (1) KR20070110050A (fr)
CN (2) CN101700498B (fr)
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WO (1) WO2006085531A1 (fr)

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CN104014373A (zh) * 2014-06-09 2014-09-03 浙江科技学院 一种丙烯二聚合成2,3-二甲基丁烯的负载型催化剂及其制备方法

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JPWO2006085531A1 (ja) 2008-06-26
CN101115558B (zh) 2011-12-07
CN101700498A (zh) 2010-05-05
US20080281139A1 (en) 2008-11-13
CN101700498B (zh) 2012-05-02
SG158844A1 (en) 2010-02-26
KR20070110050A (ko) 2007-11-15
EP1872853A1 (fr) 2008-01-02
CN101115558A (zh) 2008-01-30
JP5419348B2 (ja) 2014-02-19
EP1872853A4 (fr) 2009-04-15

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